Binder compositions with polyvalent phosphorus crosslinking agents

ABSTRACT

An fibrous insulation product is provided that includes a binder comprising a polyol and a phosphorus crosslinking agent derived from a phosphonic or phosphoric acid, salt, ester or anhydride to form crosslinked phosphodiester linkages. The polyol is polyvalent, but may be monomeric or preferably polymeric; and may be synthetic or natural in origin. Carbohydrate polysaccharides are exemplary polyols, including water-soluble polysaccharides such as dextrin, maltodextrin, starch, modified starch, etc. Additionally, the carbohydrate polymer may have a dextrose equivalent (DE) number from 2 to 20. In exemplary embodiments, the binder may also include a catalyst, a coupling agent, a process aid, and other additives. The environmentally friendly, formaldehyde-free binder may be used in the formation of residential and commercial insulation materials and non-woven chopped strand mats. A method of making fibrous products is also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No. 13/187,650, filed Jul. 21, 2011, and is related to U.S. patent application Ser. No. 12/900,540, filed Oct. 8, 2010, and its U.S. provisional patent application Ser. No. 61/250,187 entitled “Bio-Based Binders For Insulation And Non-Woven Mats” filed Oct. 9, 2009; as well as to U.S. patent application Ser. No. 12/825,375, filed Jun. 29, 2010, and its U.S. provisional patent application Ser. No. 61/221,298 entitled “Modified Starch-Based Binder” filed Jun. 29, 2009; the entire contents of each of which are expressly incorporated by reference herein.

TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION

The present invention relates generally to fibrous insulation and non-woven mats, and more particularly, to a binder for use in manufacturing fibrous mineral insulation such as fiberglass and non-woven mats that is bio-based, contains no added formaldehyde, is crosslinked through phosphate di-ester bonds, and is environmentally friendly.

BACKGROUND OF THE INVENTION

Conventional fibers are useful in a variety of applications including reinforcements, textiles, and acoustical and thermal insulation materials. Although mineral fibers (e.g., glass fibers) are typically used in insulation products and non-woven mats, depending on the particular application, organic fibers such as polypropylene, polyester, and multi-component fibers may be used alone or in combination with mineral fibers in forming the insulation product or non-woven mat.

Fibrous insulation is typically manufactured by fiberizing a molten composition of polymer, glass, or other mineral and spinning fine fibers from a fiberizing apparatus, such as a rotating spinner. To form an insulation product, fibers produced by the rotating spinner are drawn downwardly from the spinner towards a conveyor by a blower. As the fibers move downward, a binder material is sprayed onto the fibers and the fibers are collected into a high loft, continuous blanket on the conveyor. The binder material gives the insulation product resiliency for recovery after packaging and provides stiffness and handleability so that the insulation product can be handled and applied as needed in the insulation cavities of buildings. The binder composition also provides protection to the fibers from interfilament abrasion and promotes compatibility between the individual fibers.

In addition, previous workers have focused on the use of polyacrylic acid with a polyhydroxy crosslinking agent or carbohydrate-based chemistry that is linked to the Maillard reaction. See, e.g. U.S. Pat. No. 7,772,347 to Swift, et al. Polyacrylic acid binders, however, have several drawbacks. For example, polyacrylic acid binders use petroleum based materials and costs typically at least two times that of current phenolic binder systems. In addition, the high viscosity and different cure characteristics pose process difficulties. Also, Maillard reaction-based products have an undesirable dark brown color after curing. Further, the use of large amounts of ammonia needed to make the binder presents a safety risk and possible emission problems.

Hawkins, et al. in U.S. patent publication 2011/0021101, published Jan. 27, 2011 teach a formaldehyde-free binder comprising modified starches (which contain multiple hydroxyl groups) crosslinked with various reagents, including polycarboxylic acids (and their anhydrides and salts) such as citric, adipic, polyacrylic, and others. Generally this reaction is catalyzed by a phosphorous-containing catalyst or cure accelerator, such as sodium hypophosphite. However, Hawkins et al, fail to teach any phosphorus-containing compound as a crosslinking agent. A similar disclosure is found in Arkens, et al. U.S. Pat. No. 5,661,213, Arkens, et al, U.S. Pat. No. 6,221,973 and Taylor, et al. U.S. Pat. No. 6,331,350, but these also fail to teach any phosphorus-containing compound as a crosslinking agent.

In addition, phosphorus compounds are known as a flame or fire retardant and have been used in fibrous insulation products as such. U.S. Pat. No. 5,284,700 to Strauss, et al, and U.S. patent publication 2006/0178064 to Balthes, et al, are examples.

Finally, it is also known to use acids, including phosphoric acid, as a pH adjuster in various product binders, as is taught in U.S. Pat. No. 3,944,690 to Distler, et al., and U.S. Pat. No. 3,669,638 to Wong, et al.

In view of the existing problems with current binders, there remains a need in the art for a binder system that is not petroleum dependent, has no added formaldehyde, is bio-based and environmentally friendly, and is cost competitive.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a binder composition for use in the formation of fiberglass insulation and non-woven chopped strand mats that includes a polyol crosslinked with at least one phosphorus crosslinking agent. The polyol and crosslinking agent form a polyester thermoset resin, more specifically a phosphodiester crosslinked resin.

The polyol is polyvalent, meaning polyhydroxy or having two or more hydroxyl groups available for reaction. The polyol may be monomeric or polymeric; and may be natural or synthetic. In some embodiments, the polyol may be a water-soluble polysaccharide selected from pectin, dextrin, maltodextrin, starch, modified starch, starch derivatives and combinations thereof. The carbohydrate may have a dextrose equivalent (DE) from 2 to 20. In other embodiments, the polyol may be smaller monomeric compounds like glycerol, ethylene glycol, erythritol, pentaeythritol, or triethanoloamine (TEA), or it may be polymeric like polyvinyl alcohol, polyethylene glycol, polyol- or hydroxyl-functionalized acrylic resins, or di-, tri- and polysaccharides.

The phosphorus crosslinking agent is also polyvalent, meaning it will have two or more reactive sites. It may be selected from phosphonic acid; a salt, ester or anhydride of phosphonic acid; phosphoric acid; a salt, ester or anhydride of phosphoric acid; and mixtures thereof. With only one reactive hydroxyl, phosphinic acid and its salts and esters are generally not suitable. For example, the phosphorus crosslinking agent may have the formula I

wherein ˜Y represents either a double bonded oxygen or a lone pair of electrons; R¹ and R² are independently selected from OH, OR⁴, O(CO)R⁴, or O⁻M⁺; and R³ is selected from H, OH, R⁴, OR⁴, O(CO)R⁴, O⁻M⁺or OR⁵;

-   -   wherein R⁴ is (C₁-C₅)alkyl, (C₁-C₅)alkenyl, (C₁-C₅)alkynyl, or         aryl; M⁺ is a cation representing an ionizable salt; and R⁵         represents 1 to 5 additional phosphonate moieties

In some exemplary embodiments, the binder composition may include a catalyst, a silane coupling agent, a moisture resistance agent and/or a pH adjuster or other additives. The binder composition is free of added formaldehyde and is environmentally friendly.

The invention comprises both methods of binding fibrous materials using these binder compositions, as well as the fibrous products bound or crosslinked with phosphodiester linkages caused by use of these binder compositions.

It is another object of the present invention to provide a fibrous insulation product that includes a plurality of randomly oriented fibers and a binder composition applied to at least a portion of the fibers and interconnecting the fibers. The binder composition may be any of those described above and may also include one or more members selected from a catalyst, a coupling agent, a process aid, a crosslinking density enhancer, an extender, a moisture resistant agent, a dedusting oil, a colorant, a corrosion inhibitor, a surfactant, and a pH adjuster.

It is yet another object of the present invention to provide a non-woven chopped strand mat formed of a plurality of randomly oriented glass fibers having a discrete length enmeshed in the form of a mat having a first major surface and a second major surface and a binder composition at least partially coating the first major surface of the mat. The binder composition is as described above and may also include one or more members selected from a catalyst, a moisture resistant agent, and a pH adjuster. In at least one exemplary embodiment, the binder includes a carbohydrate polyol that is a water-soluble polysaccharide selected from pectin, dextrin, maltodextrin, starch, modified starch, starch derivatives and combinations thereof.

It is an advantage of the present invention that the carbohydrate is natural in origin and derived from renewable resources.

It is yet another advantage of the present invention that maltodextrin is readily available and is low in cost.

It is a further advantage of the present invention that insulation products and non-woven mats utilizing the inventive binder composition can be manufactured using current manufacturing lines, thereby saving time and money.

It is another advantage of the present invention that the binder composition has no added formaldehyde.

It is a further advantage of the present invention that the binder composition has a reduction in particulate emission compared to conventional phenol/urea/formaldehyde binder compositions.

It is a feature of the present invention that the maltodextrin can form an aqueous mixture that can be applied by conventional binder applicators, including spray applicators.

It is a further feature of the present invention that the binder can be acidic, neutral, or even basic in the case of an ammonium salt of a phosphorus-based crosslinking agent.

It is another feature of the present invention that the inventive insulation products and non-woven mats have no added formaldehyde.

It s also a feature of the invention that the inventive binder composition can be useful for composite reinforcements, such as chopped strands, for use in thermoplastics, thermosets, and roofing applications. In addition, the inventive binders may be used in both single and multi-end rovings.

The foregoing and other objects, features, and advantages of the invention will appear more fully hereinafter from a consideration of the detailed description that follows. It is to be expressly understood, however, that the drawings are for illustrative purposes and are not to be construed as defining the limits of the invention.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. All references cited herein, including published or corresponding U.S. or foreign patent applications, issued U.S. or foreign patents, and any other references, are each incorporated by reference in their entireties, including all data, tables, figures, and text presented in the cited references.

It is to be noted that the phrase “binder”, “bio-based binder”, “binder composition”, and “binder formulation” may be used interchangeably herein. “Crosslinking agent,” unless context dictates otherwise, means a polyvalent phosphorus-based crosslinking agent, such as one based on phosphorous acid, phosphonic acid or phosphoric acid, or having one or more of those functional moieties.

The present invention relates to environmentally friendly, aqueous phosphodiester binder compositions that contain at least one polyol and at least one polyvalent phosphorus crosslinking component; and to fibrous products manufactured with such a binder composition; and to methods of manufacture.

Polyol Component

By definition, the polyol is polyvalent, meaning polyhydroxy or having two or more hydroxyl groups that can be available for reaction. While a polyol has a minimum of two hydroxyl groups, there is no theoretical maximum number of hydroxyl groups. Diols, triols, tetraols, penta-ols, hexa-ols and higher polyols are all encompassed, particularly in polymeric compounds. The polyol may be monomeric or polymeric; and may be natural or synthetic. In some embodiments, the polyol may be smaller monomeric compounds like glycerol, ethylene glycol, propanediols, propanetriols, trimethylol propane, erythritol or other butane-based polyols, pentaeythritol, triethanoloamine (TEA), or 1,2,6-hexane-triol; or any monosaccharide having at least 4 carbons, including pentoses, and hexoses, including, but not limited to erythrose, erythulose, threose, ribose, ribulose, arabinose, xylose, xylulose, glucose, dextrose (or D-glucose), mannose, glactose, fructose, and sorbose. All isomeric and stereochemical forms of these monosaccharides are encompassed in the invention. Furthermore, derivatives of saccharides may also be suitable, provided they retain their polyvalent polyol nature after derivatization. Thus, the polyol may include O-glycosides, N-glycosides, O-alkyl (e.g. methyl, ethyl), O-acylated sugars, amino sugars, sugar alcohols (like sorbitol, xylitol, erythritol, etc.) and the like.

In other embodiments, the polyol may be a synthetic or naturally occurring polymer, such as polyvinyl alcohol, poly(ether) polyols, poly(ester) polyols, polyethylene glycol, polyol- and hydroxy-functional acrylic resins such as JONCRYL® (BASF Resins), MACRYNAL® (Cytec Industries) PARALOID® (Dow Coating Materials), G-CURE®, TSAX® and SETALUX® (Nuplex Resins, LLC) in solution or emulsion form; or di-, tri- and higher polysaccharides. Some common exemplary disaccharides include maltose, sucrose, lactose, cellobiose and trehalose. Other polysaccharides include polysaccharides selected from pectin, dextrin, maltodextrin, starch, modified starch, starch derivatives, glycans, dextrins, fructans, chitin and combinations thereof that can be dispersed in water. Dispersions in water include emulsions, suspensions, colloids and true solutions. When used, a polysaccharide may have a dextrose equivalent (DE) from 2 to 20.

Due to the wide variability in molecular weights of the polyol component and (as discussed below) the crosslinking agent, the weight ratios of the various components of the binder composition can vary tremendously. Thus, polyol component may be present in the binder composition in an amount from about 1% to about 99% by weight of the total solids in the binder composition, more likely from about 20% to about 99% by weight of the total solids in the binder composition. As used herein, % by weight indicates % by weight of the total solids in the binder composition.

In some exemplary embodiments, the saccharide polyol component is a carbohydrate and the binder and includes a carbohydrate and a crosslinking agent. In some exemplary embodiments, the carbohydrate-based binder composition also includes a coupling agent, a process aid agent, an extender, a pH adjuster, a catalyst, a crosslinking density enhancer, a deodorant, an antioxidant, a dust suppressing agent, a biocide, a moisture resistant agent, or combinations thereof. The binder may be used in the formation of insulation materials and non-woven chopped strand mats. In addition, the binder is free of added formaldehyde. Further, the binder composition has a reduction in particulate emission compared to conventional phenol/urea/formaldehyde binder compositions. The inventive binder may also be useful in forming particleboard, plywood, and/or hardboards.

In one or more exemplary embodiment, the binder includes at least one carbohydrate that is natural in origin and derived from renewable resources. For instance, the carbohydrate may be derived from plant sources such as legumes, maize, corn, waxy corn, sugar cane, milo, white milo, potatoes, sweet potatoes, tapioca, rice, waxy rice, peas, sago, wheat, oat, barley, rye, amaranth, and/or cassava, as well as other plants that have a high starch content. The carbohydrate polymer may also be derived from crude starch-containing products derived from plants that contain residues of proteins, polypeptides, lipids, and low molecular weight carbohydrates. The carbohydrate may be selected from monosaccharides (e.g., xylose, glucose/dextrose, and fructose), disaccharides (e.g., sucrose, maltose, and lactose), oligosaccharides (e.g., glucose syrup and fructose syrup), and polysaccharides (e.g., pectin, dextrin, maltodextrin, starch, modified starch, and starch derivatives), provided they can be prepared as water dispersions, which includes emulsions, suspensions, colloids and true solutions.

The carbohydrate polymer may have a number average molecular weight from about 1,000 to about 8,000. Additionally, the carbohydrate polymer may have a dextrose equivalent (DE) number from 2 to 20, from 7 to 11, or from 9 to 14. The carbohydrate dispersions beneficially have a low viscosity and cure at moderate temperatures (e.g., 80-250° C.) alone or with additives. The low viscosity enables the carbohydrate to be utilized in a binder composition. In exemplary embodiments, the viscosity of the carbohydrate dispersion may be lower than 500 cps at 50% concentration and between 20 and 30° C. The use of a carbohydrate in the inventive binder composition is advantageous in that carbohydrates are readily available or easily obtainable and are low in cost.

In at least one exemplary embodiment, the carbohydrate is a water-soluble polysaccharide such as dextrin or maltodextrin. The carbohydrate polymer may be present in the binder composition in an amount from about 40% to about 95% by weight of the total solids in the binder composition, from about 50% to about 95% by weight of the total solids in the binder composition, from about 60% to about 90%, or from about 70% to about 85%.

Polyvalent Phosphorus Component

A polyvalent phosphorus compound serves as a crosslinking agent. A polyvalent phosphorus crosslinker compound may be represented by formula I:

wherein ˜Y represents either a double bonded oxygen (═O) or a lone pair of electrons; R¹ and R² are independently selected from OH, OR⁴, O(CO)R⁴, or O⁻M⁺; and R³ is selected from H, OH, R⁴, OR⁴, O(CO)R⁴, O⁻M⁺or OR⁵;

-   -   wherein R⁴ is selected from (C₁-C₅)alkyl, (C₁-C₅)alkenyl,         (C₁-C₅)alkynyl, or aryl; M⁺ is a cation representing an         ionizable salt; and wherein R⁵ represents 1 to 5 additional         phosphonate moieties; or a polymeric backbone of 1-20 carbons         between phosphonate moieties.

As used herein, the term “(C₁-C₅)alkyl” refers to a straight-chain and branched non-cyclic saturated hydrocarbon having from 1 to 5 carbon atoms. Representative straight chain —(C₁-C₅)alkyl groups include methyl, -ethyl, -n-propyl, -n-butyl, and -n-pentyl. Representative branched-chain —(C₁-C₅)alkyl groups include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, and 1,2-dimethylpropyl.

As used herein, the term “(C₂-C₅)alkenyl” refers to straight chain and branched non-cyclic hydrocarbons having from 2 to 5 carbon atoms and including at least one carbon-carbon double bond. Representative straight chain and branched —(C₂-C₅)alkyenyl groups include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, and -2-methyl-2-butenyl.

As used herein, the term “—(C₂-C₅)alkynyl” refers to straight chain and branched non-cyclic hydrocarbons having from 2 to 5 carbon atoms and including at least one carbon-carbon triple bond. Representative straight chain and branched —(C₂-C₅)alkynyl groups include -acetylenyl, -propynyl, -1 butynyl, -2-butynyl, -1-pentynyl, -2-pentynyl, -3-methyl-1-butynyl, and -4-pentynyl.

As used herein, the term “-aryl” refers to phenyl; phenyl optionally substituted with up to three groups independently selected from (C₁-C₅)alkyl, (C₁-C₅)alkenyl, (C₁-C₅)alkynyl, hydroxyl, amino, nitro, or halo groups.

As used herein, the term “phosphonate moiety” refers to —P(O)(OH)O—, optionally terminated by H or a cation; also represented as the portion within the brackets in structure C in Table 1 below.

It should be recognized that formula I represents several types of phosphorus-containing crosslinking agents: (a) phosphorous acid and its phosphite derivatives when Y is a lone pair of electrons, as shown by structure A in Table 1 below; (b) phosphonic acid and its phosphonate derivatives when X is ═O, R¹ and R² are both OH and R³ is H or R⁴ or other possibilities (see structure B); (c) phosphoric acid and its phosphate derivatives when X is ═O and R¹, R² and R³ are all OH (see structure B); (d) polyphosphoric acids when X is ═O, R¹ and R² are OH, R³ is OR⁵, and R⁵ is additional phosphonate moieties (see structure C, wherein n represents an integer from 1 to 6); and (e) polymeric phosphonates when X is ═O, R¹ and R² are OH, R³ is OR⁵, and R⁵ is a polymeric backbone of 1-20 carbons (see structure D, representing a dimer). Such polymeric backbones have been prepared from styrene monomers by Kim, et al, Characterization of Poly(styrene-b-vinylbenzylphosphonic acid) Copolymer by Titration and Thermal Analysis, Macromolecular Research, Vol. 15, No. 6, pp 587-594 (2007), which is incorporated herein by reference. The backbone may be akyl, alkenyl, or aryl, or mixed; it may include substitutions and linkers with atoms and moieties like oxygen, carbonyl, and amines to improve synthesis and solubility, if desired.

TABLE 1 Representative phosphorus structures

A

B

C

D

Note that the lone pair of electrons (represented by the two dots in Structure A) and the double bonded oxygen exert their presence to make these molecules generally tetrahedral about the phosphorus atom and, apart from that asymmetry, substituents at R¹, R² and R³ are all equivalent positions. Table 2 offers some exemplary substituents for base formulas.

TABLE 2 Exemplary substituents and conventional nomenclature (not all are polyvalent) R¹ R² R³ Name(s) OR⁴ OR⁴ H or R⁴ phosphonite H₃PO₃ OH OH OH phosphorous acid or OH O⁻M⁺, OR⁴ OH orthophosphorous acid, but also or OC(O)R⁴ phosphonic acid since this O⁻M⁺, OR⁴ O⁻M⁺, OR⁴ OH tautomerically rearranges to or OC(O)R⁴ or OC(O)R⁴ a dihydroxy form (see H₃PO₃ below); phosphites OH OH OR⁵ H₃PO₂ H or R⁴ OH H or R⁴ phosphinic acid (not polyvalent) hypophosphorous acid, but see above re nomenclature confusion (not polyvalent) H or R⁴ O⁻M⁺, OR⁴ H or R⁴ phosphinate or OC(O)R⁴ hypophosphite H₃PO₃ OH OH H or R⁴ phosphonic acid or orthophosphorous acid O⁻M⁺, OR⁴ O⁻M⁺, OR⁴ H or R⁴ phosphonates, sometimes also or OC(O)R⁴ or OC(O)R⁴ phosphites (salt, ester or anhydride) OH OH OR⁵ where R⁵ polyphosphoric acid is polymeric backbone H₃PO₄ OH OH OH phosphoric acid O⁻ O⁻ O⁻ phosphate ion (−3 uncommon) O⁻ O⁻ OR⁴ phosphate ester ion (−1, −2) OR⁴ O⁻ OR⁴ O⁻M⁺, OR⁴ O⁻M⁺, OR⁴ OR⁴ phosphate salt, ester or anhydride or OC(O)R⁴ or OC(O)R⁴ OH OH OR⁵ where R⁵ polyphosphoric is additional phosphonate moieties

As seen from Table 2 above, the polyvalent forms of phosphorus include H₃PO₃ (both valency states: i.e. phosphorous acid and phosphonic acid) and H₃PO₄ (phosphoric acid), as well as salts, esters, anhydrides and various derivatives of these. Phosphinic or hypophosphorous acid and its derivatives are not polyvalent.

Salts are formed when one or more hydrogen atoms are dissociated from hydroxyl group(s) and are replaced by a cation (M⁺). Depending on the charge of the cation, there may be one or two phosphorus complexes per cation. Classic salts formed by alkali metals like sodium, potassium, calcium or magnesium do not perform as well as the ammonium salts, formed by the cation N⁺R₃, wherein each R is independently selected from H, (C₁-C₅)alkyl (alkylamines) or (C₁-C₅)alkyl substituted with hydroxyl (alkanolamines). Preferred ammonium salts can be formed with primary, secondary or tertiary amines. It may be particularly useful to utilize alkanolamines, since the hydroxyl function of these cations may provide crosslinking density enhancement (discussed below).

Phosphoesters are formed when one or more hydrogen atoms are dissociated from hydroxyl group(s) and are replaced by alkoxy groups, (RO—). Anhydrides are formed when one or more hydrogen atoms are dissociated from hydroxyl group(s) and are replaced by acyl groups, (RC(O)—).

The polyvalent phosphorus crosslinking agent has a number average molecular weight greater than 80, from about 80 to about 24,000, or from about 80 to about 300 in the case of monomeric phosphorus crosslinkers; and from about 200 to about 24,000 in the case of polymeric phosphorus crosslinkers. In some exemplary embodiments, the crosslinking agent has a number average molecular weight less than about 1000. Non-limiting examples of suitable crosslinking agents include phosphoric acid, ammonium phosphate, ammonium phosphonate, and polyphosphoric acid.

The crosslinking agent may be present in the binder composition in an amount from about 1% to about 99% by weight of the binder composition. The wide range is due, in part, to the broad variability in molecular weights of both the polyol and the phosphorus crosslinking agent. In exemplary embodiments, the crosslinking agent may be present in the binder composition in an amount from about 1% to about 40% by weight of the total solids in the binder composition or from about 1% to about 20% by weight. For example, when the polyol is a maltodextrin polyol with a DE for 2-10 and the polyvalent crosslinking agent is a small molecule (e.g. phosphoric acid, phosphonic acid, phosphorous acid or polyphosphoric acid), the polyol component may be present in an amount from about 60% to about 95% while the phosphorus crosslinking agent may be present in an amount from about 5% to about 40% of the total solids weight.

Optionally, the binder composition may include a catalyst to assist in the crosslinking, however, an advantage of the present invention is that no catalyst is required. If desired, optional catalysts may include inorganic salts, Lewis acids (i.e., aluminum chloride or boron trifluoride), Bronsted acids (i.e., sulfuric acid, p-toluenesulfonic acid and boric acid) organometallic complexes (i.e., lithium carboxylates, sodium carboxylates), Lewis bases (i.e., polyethyleneimine, diethylamine, or triethylamine); and/or an alkali metal salt of a phosphorus-containing organic or inorganic acid (e.g. sodium hypophosphite), or any catalyst described further in the literature, including U.S. patent application Ser. No. 12/900,540.

The catalyst or cure accelerator, when used, may be present in the binder composition in an amount from about 0.5% to about 10% by weight of the total solids in the binder composition, or from about 2.0% to about 8.0% by weight, or from about 3.0% to about 6.0% by weight.

The binder composition may optionally contain at least one coupling agent. In at least one exemplary embodiment, the coupling agent is a silane coupling agent. The coupling agent(s) may be present in the binder composition in an amount from about 0.01% to about 5.0% by weight of the total solids in the binder composition, from about 0.01% to about 2.5% by weight, or from about 0.1% to about 0.5% by weight. Non-limiting examples of silane coupling agents that may be used in the binder composition may be found in the literature, including U.S. patent application Ser. No. 12/900,540.

In addition, the binder composition may include a process aid in addition to the carbohydrates described above. The process aid is not particularly limiting so long as the process aid functions to facilitate the processing of the fibers formation and orientation. The process aid can be used to improve binder application distribution uniformity, to reduce binder viscosity, to increase ramp height after forming, to improve the vertical weight distribution uniformity, and/or to accelerate binder de-watering in both forming and oven curing process. The process aid may be present in the binder composition in an amount from about 0% to about 25.0% by weight, from about 1.0% to about 20.0% by weight, or from about 5.0% to about 15.0% by weight.

Examples of processing aids include viscosity modifiers and defoaming agents (e.g., emulsions and/or dispersions of mineral, paraffin, or vegetable oils, dispersions of polydimethylsiloxane (PDMS) fluids and silica which has been hydrophobized with polydimethylsiloxane or other materials, and particles made of amide waxes such as ethylenebis-stearamide (EBS) or hydrophobized silica). A further process aid that may be utilized in the binder composition is a surfactant. One or more surfactant may be included in the binder composition to assist in binder atomization, wetting, and interfacial adhesion. Surfactants are not particularly limiting and are described in the literature, including U.S. patent application Ser. No. 12/900,540.

The binder composition may optionally include a corrosion inhibitor to reduce or eliminate any potential corrosion to the process equipment. The corrosion inhibitor may be present in the binder composition in an amount from about 0% to about 15.0% by weight, from about 1.0% to about 5.0% by weight, or from about 0.2% to about 1.0% by weight.

Also, the binder composition may also contain one or more biocide to reduce or eliminate mold and fungal growth on the fiberglass product. The biocide may be present in the binder composition in an amount from about 0% to about 10.0% by weight, from about 0.05% to about 1.0% by weight, or from 0.1% to about 0.5% by weight.

In some embodiments, a higher degree of crosslinking is desired, such as for improving stiffness or insulation R-value. In such cases, the binder composition may optionally include a crosslinking density enhancer to improve the degree of crosslinking of the polyol-based phosphodiester binder. Crosslinking density enhancement can be achieved by at least two mechanism: (a) increasing esterification between the functional hydroxyl and polyvalent phosphorus component and/or (b) introducing free radical linkages to improve the strength of the thermoset resin. The esterification crosslinking density can be adjusted by selecting polyols and/or polyvalent phosphorus crosslinking agents that include a more functional moieties per weight; by altering the ratio between hydroxyl and polyvalent phosphorus component; and/or adding additional esterifiable functional groups such as triethanolamine, diethanolamine, mono ethanolamine, 1-amino-2-propanol, 1,1′-aminobis,-2-propanol, 1,1,′1″nitrilotri-2-propanol, 2-methylaminoethanol, 2-dimethylaminoethanol, 2-(2-aminoethoxy)ethanol, 2{(2aminoethyl)amino}ethanol, 2-diethylaminoethanol, 2-butylaminoethanol, 2-dibutylaminoethanol, 2cyclohexylaminoethanol, 2,2′-(methylamino)bis-ethanol, 2,2′-(butylamino)bis-ethanol, 1-methylamino-2propanol, 1-dimethylamino-2-propanol, 1-(2-aminoethylamino)-2-propanol, 1,1′-(methylimino)bis-2-propanol, 3-amino-1-propanol, 3-dimethylamino-1-propanol, 2-amino-1-butanol, I-ethylamino-2-butanol, 4-diethylamino-1-butanol, 1-diethylamino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 2,2-dimethyl-3-dimethylamino-1-propanol, 4-diethylamino-2-butyn-1-ol, 5-diethylamino-3-pentyne-2-ol, bis (2-hydroxypropyl)amine, as well as other alkanolamines, their mixtures, and their polymers.

The other method to enhance crosslinking density is to use both esterification and a free radical reaction for the crosslinking reactions, to form an interpenetrating polymer. A simple free radical reaction is illustrated by the adduct formed across the double bonds of alkenes, such as the vinyl moiety. Thus, vinyl or styrene substituents or polymers bearing the polyvalent phosphorus are capable of enhancing crosslinking density. Chemicals that can be used for both esterification and free radical reactions include maleic anhydride, maleic acid, or itaconic acid. The crosslinking density enhancer, when used, may be present in the binder composition in an amount from about 0.5% to about 25.0% by weight, from about 1.0.0% to about 20.0% by weight, or from about 5.0% to about 15.0% by weight.

The binder may also include organic and/or inorganic acids and bases in an amount sufficient to adjust the pH to a desired level. The pH may be adjusted depending on the intended application, or to facilitate the compatibility of the ingredients of the binder composition. Although phosphorus acids are already very acidic, some pH adjusters may be utilized to adjust the pH of the binder composition to an acidic pH. Examples of suitable acidic pH adjusters include sulfuric acid and p-toluenesulfonic acid and their corresponding salts. Alternatively, for pH adjustment toward the basic side, organic and/or inorganic bases, such sodium hydroxide, ammonium hydroxide, and diethylamine, and any kind of primary, secondary, or tertiary amine (including alkanol amine), can be used. Ammonium salts help move the acidic phosphorus crosslinkers toward neutral or basic pH; and can be used to balance pH to values between 2 and 9. The pH of the binder composition, when in an acidic state, may range from about 1 to about 6, and in some exemplary embodiments, from about 1 to about 3, including all amounts and ranges in between. The pH adjuster in an acidic binder composition may be present in the binder composition in an amount sufficient to obtain the desired pH.

The binder composition may also contain a moisture resistance agent, such as a alum, aluminum sulfate, latex, a silicon emulsion, a hydrophobic polymer emulsion (e.g., polyethylene emulsion or polyester emulsion), and mixtures thereof. In at least one exemplary embodiment, the latex system is an aqueous latex emulsion. The latex emulsion includes latex particles that are typically produced by emulsion polymerization. In addition to the latex particles, the latex emulsion may include water, a stabilizer such as ammonia, and a surfactant. The moisture resistance agent may be present in the binder composition in an amount from 0% to about 20% by weight of the total solids in the binder composition, from about 5.0% to about 10% by weight, or from about 5.0% to about 7.0% by weight.

Additionally, the binder may contain a dust suppressing agent to reduce or eliminate the presence of inorganic and/or organic particles which may have adverse impact in the subsequent fabrication and installation of the insulation materials. The dust suppressing agent can be any conventional mineral oil, mineral oil emulsion, natural or synthetic oil, bio-based oil, or lubricant, such as, but not limited to, silicone and silicone emulsions, as well as any petroleum or non-petroleum oil with a high flash point to minimize the evaporation of the oil inside the oven.

In addition, the binder may optionally include at least one extender to improve the binder's appearance and/or to lower the overall manufacturing cost. The extender can be an inorganic filler, such as tin oxide or talc or organic materials such as lignin, lignin sulfonate, or a protein-based biomass. In exemplary embodiments, the extender is a protein-containing biomass. Like the carbohydrate, the protein-containing biomass is natural in origin and is derived from renewable resources. For instance, the protein may be derived from plant sources such as soy (e.g., a soy flour), peanuts, sunflowers, kidney beans, walnuts, or from other plants that have a high protein content. Alternatively, the protein may come from animal sources such as, but not limited to, eggs, blood, and animal tissue (e.g., beef, pork, or chicken, as well as fish). The protein-containing biomass may contain up to about 95% protein, and in exemplary embodiments, up to 90%, 75%, or 50% protein. As used herein, the term “protein” may be defined as a macromolecule composed of one or more polypeptides and includes any combination of polypeptides regardless its amino acid sequence. In addition, the term “protein” is intended to include all possible structures in which a protein can be obtained naturally or a protein that has been modified to improve its reactivity. It is to be appreciated that derivatives of natural proteins and synthetic proteins are also included within the scope of the term “protein”. In one or more exemplary embodiment, the protein-containing biomass is soy flour. The extender may be present in the binder composition in an amount from about 0% to about 70.0% by weight of the total solids in the binder composition, from about 5.0% to about 50.0% by weight, or from about 10.0% to about 40.0% by weight.

The binder may optionally contain conventional additives such as, but not limited to dyes, pigments, fillers, colorants, UV stabilizers, thermal stabilizers, anti-foaming agents, anti-oxidants, emulsifiers, preservatives (e.g., sodium benzoate), corrosion inhibitors, and mixtures thereof. Other additives may be added to the binder composition for the improvement of process and product performance. Such additives include lubricants, wetting agents, surfactants, antistatic agents, and/or water repellent agents. Additives may be present in the binder composition from trace amounts (such as <about 0.1% by weight the binder composition) up to about 10.0% by weight of the total solids in the binder composition. In some exemplary embodiments, the additives are present in an amount from about 0.1% to about 5.0% by weight of the total solids in the binder composition, from about 1.0% to about 4.0% by weight, or from about 1.5% to about 3.0% by weight.

The binder further includes water to dissolve or disperse the active solids for application onto the reinforcement fibers. Water may be added in an amount sufficient to dilute the aqueous binder composition to a viscosity that is suitable for its application to the reinforcement fibers and to achieve a desired solids content on the fibers. In particular, the binder composition may contain water in an amount from about 50% to about 98.0% by weight of the total solids in the binder composition.

The binder composition may be made by dissolving or dispersing the crosslinking agent in water to form a mixture. Next, the polyol may be mixed with the crosslinking agent in the mixture to form the binder composition. If desired, a cure accelerator (i.e., catalyst) may be added to the binder composition, as well as other possible additives. The binder composition may be further diluted with water to obtain a desired amount of solids. If necessary, the pH of the mixture may be adjusted to the desired pH level with organic and inorganic acids and bases.

The binder composition may be applied to fibrous products in an amount from about 1% to 40% by weight of the total fibrous product, depending on the nature and use of the product. Binder content of the fibrous products is typically measured by loss on ignition or “LOI” of the cured product. For some lighter weight insulation products, such as residential insulation, the binder content may be from about 1% to about 15% by weight LOI; or from about 2% to about 12%. For other products, such as higher density industrial and commercial products, more binder may be applied, for example from about 2% to about 40% by weight LOI; more usually from about 2% to about 20% or from about 3% to about 20%.

Fibrous Products with Phosphorus-Based Binders

The manufacture of glass fiber insulation products is well characterized in the patent literature and need not be described here. See, for example, Hawkins, et al. in U.S. patent publication 2011/0021101, published Jan. 27, 2011, which in incorporated herein in its entirety.

In one exemplary embodiment, the binder composition is used to form a fibrous product, typically an insulation product. Fibrous products are generally formed of matted inorganic fibers bonded together by a cured thermoset polymeric material. Examples of suitable inorganic fibers include glass fibers, wool glass fibers, and ceramic fibers. Optionally, other reinforcing fibers such as natural fibers and/or synthetic fibers such as polyester, polyethylene, polyethylene terephthalate, polypropylene, polyamide, aramid, and/or polyaramid fibers may be present in the insulation product in addition to the glass fibers. The term “natural fiber” as used in conjunction with the present invention refers to plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or phloem. Examples of natural fibers suitable for use as the reinforcing fiber material include basalt, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and combinations thereof. Insulation products may be formed entirely of one type of fiber, or they may be formed of a combination of types of fibers. For example, the insulation product may be formed of combinations of various types of glass fibers or various combinations of different inorganic fibers and/or natural fibers depending on the desired application for the insulation. The embodiments described herein are with reference to insulation products formed primarily of glass fibers.

The term “fibrous products” is general and encompasses a variety of compositions, articles of manufacture, and manufacturing processes. “Fibrous products” may be characterized and categorized by many different properties; density for example, which may range broadly from about 0.2 pounds/cubic foot (“pcf”) to as high as about 10 pcf, depending on the product. Low density flexible insulation batts and blankets typically have densities between about 0.2 pcf and about 5 pcf, more commonly from about 0.3 to about 4 pcf. Fibrous products also include higher density products having densities from about 1 to about 10 pcf, more typically from about 2 or 3 pcf to about 8 pcf, such as boards and panels or formed products. Higher density insulation products may be used in industrial and/or commercial applications, including but not limited to metal building insulation, pipe or tank insulation, insulative ceiling and wall panels, duct boards and HVAC insulation, appliance and automotive insulation, etc.

Another property useful for categorization is the rigidity of the product. Residential insulation batts are typically quite flexible and they can be compressed into rolls or batts while recovering their “loft” upon decompression. In contrast, other fibrous products, such as ceiling tiles, wall panels, foundation boards and certain pipe insulation to mention a few, are quite rigid and inflexible by design. These products will flex very little and are unlikely to be adapted or conformed to a particular space.

Shape is another important property. Some fibrous products are flexible, as noted and can be forced to assume conforming shapes, while other are formed and shaped for a specific purpose. In some embodiments, the shape is substantially planar, as in duct boards, ceiling tiles and some wall insulation. In other embodiments, the fibrous insulation product is manufactured with a particular shape (e.g. cylindrical) suitable for a particular size conduit, pipe or tank. In other cases, specific shapes and cutouts, often die-cut, are included in certain appliance insulation products, automotive insulation products and the like. Finally, other shapes may be created with nonwoven textile insulation products.

Other classifications of fibrous insulation products can include the method of manufacture. The manufacture of glass fiber insulation may be carried out in a continuous process by rotary fiberization of molten glass, immediately forming a fibrous glass pack on a moving conveyor. The glass fibers, while in transit in the forming chamber to the conveyor and while still hot from the fiberization operation, are sprayed with the inventive aqueous binder composition so as to result in a distribution of the binder composition throughout the formed insulation pack of fibrous glass. Cooling water may also be applied to the glass fibers in the forming chamber prior to the application of the aqueous binder composition.

The fibrous insulation pack is then heated, such as by a curing oven where heated air is blown through the insulation pack to evaporate any remaining water in the binder, cure the binder, and rigidly bond the fibers together. The cured binder imparts strength and resiliency to the insulation blanket. It is to be appreciated that the drying and curing of the binder may be carried out in either one or two different steps. The two stage (two-step) process is commonly known as B-staging.

A significant portion of the insulation placed in the insulation cavities of buildings is in the form of insulation blankets rolled from insulation products such as is described above. Faced insulation products are installed with the facing placed flat on the edge of the insulation cavity, typically on the interior side of the insulation cavity. Insulation products where the facing is a vapor retarder are commonly used to insulate wall, floor, or ceiling cavities that separate a warm interior space from a cold exterior space. The vapor retarder is placed on one side of the insulation product to retard or prohibit the movement of water vapor through the insulation product.

Formed or shaped products may include a further step, optionally during cure, that molds or shapes the product to its specific final shape. Rigid boards are a type of shaped product, the shape being planar. Other shaped products may be formed by dies or molds or other forming apparatus. Rigidity may be imparted by the use of higher density of fibers and/or by higher levels of binder application. As an alternative to rotary fiberizing, some fibrous insulation products, particularly higher density, non-woven insulation products, may be manufactured by an air-laid or wet-laid process using premade fibers of glass, other minerals or polymers that are scattered into a random orientation and contacted with binder to form the product.

In another embodiment of manufacture, the binder composition may be used in combination with pre-manufactured fibers to form a non-woven chopped strand mat. In particular, binder is added during the formation of the chopped strand mat in a wet-laid or air-laid mat processing line, where the fibers are dispersed by a water (or air) fluid. It is to be appreciated that reference is made herein to glass fibers, although the chopped strand mat could be formed of, or include, non-glass fibers. Air laid and wet-laid processes are well known to those skilled in the art. The inventive binder composition is applied to the web by a suitable binder applicator, such as a spray applicator or a curtain coater. As with rotary fiberization, once the binder has been applied to the mat, the binder coated mat is passed through at least one drying oven to remove any remaining water and cure the binder composition. The formed non-woven chopped strand mat that emerges from the oven is an assembly of randomly oriented, dispersed, individual glass fibers. The chopped strand mat may be rolled onto a take-up roll for storage for later use. The non-woven mat can be use in roofing, flooring, ceiling, wall applications, as filters, in ground based vehicles, and in aircraft.

Whereas examples 4, 5, 7, and 12 below relate to flexible, light density residential insulation, examples 8, 9 and 10 further illustrate commercial fibrous products other than the typical flexible residential insulation. A more complete listing of non-residential insulation fibrous products that can be manufactured using the binder composition according to the invention is set forth in Table 3, below.

TABLE 3 Selected Commercial and Industrial Fibrous Products which may use a Phosphorus-Based Binder Flexible, Light Density Rigid Pipe Insulation Textile E-glass Rigid Boards Insulation and pipe rolls Nonwoven Density Wide range of densities- Light density - Ranging from 0.3 to Ranging from 3-6 pcf Ranging from 0.8 to 4 pcf from 1.5 to 10 pcf 4.0 pcf Binder content about 2 to about 20% about 2 to about 13% LOI about 3 to about 15% LOI about 5 to about 20% LOI LOI Manufacturing Rotary fiber forming Rotary fiber forming process Rotary fiber forming Air-laid nonwoven process method process process plus on or offline molding/pipe formation process Exemplary QUIET R Duct Board Certified R Metal Building EVOLUTION Paper-Free QUIET R Textile Duct Owens Corning QUIET R Duct Liner Insulation ASJ Liner Products Board ELAMINATOR ® Pre-Engineered VAPORWICK Insulation DURAFLEX 700 Series Insulation Metal Roof Insulation FIBERGLAS ™ Pipe and Transportation Insul-Quick Insulation MBI Plus Tank Insulation rolls SCR Insulation Board Metal Bldg Utility Blanket Curtainwall Unfaced Metal Building Insulation QuietZone Shaftwall for Canada Warm-N-Dri Flexible Duct Media Insulation Energy Board QUIET R Rotary Duct Liner TremDrain SOFTR Duct Wrap FRK Exterior Foundation TIW Types I and II Barrier Board FLEX-Wrap for pipes and tanks Ceiling Board Blanks H2V Series RA Series Select Sound Thermorange FlameSpread 25 Sonobatts Thermal Batts

There are numerous advantages provided by the inventive binder formulations. For example, they may be used with a saccharide or carbohydrate polyol of natural origin and derived from renewable resources. By lowering or eliminating formaldehyde emission, the overall volatile organic compounds (VOCs) emitted in the workplace are reduced. Additionally, because carbohydrates are relatively inexpensive, the insulation product or chopped fiber mat can be manufactured at a lower cost. Further, the binder has low to no odor, making it more desirable to work with.

Having generally described this invention, a further understanding can be obtained by reference to certain specific examples illustrated below which are provided for purposes of illustration only and are not intended to be all inclusive or limiting unless otherwise specified.

EXAMPLES

Example 1-14 are incorporated from U.S. patent application Ser. No. 12/900,540, filed Oct. 8, 2010, incorporated herein.

Examples 15-16: Binder Preparations with Citric Acid Crosslinkers

The binder compositions set forth in Table 4 were prepared according to the following general procedure. Crosslinking agents were dissolved or dispersed in water to form a dispersion. The polyol was then mixed into the dispersion to form the binder composition. In some formulations, a cure accelerator (i.e., catalyst) was added, as well as other additives as set forth in Table 4. The binder composition is further diluted with water to obtain a desired amount of solids. The pH was measured and given in Table 4.

TABLE 4 Binder recipes (weight in percent, except total weight in grams) Example 15 Component (Control) Example 16 Maltodextrin 6.52 5.51 (as polyol) Crosslinker Citric Acid Citric Acid 1.63 1.63 85% Phosphoric Acid 1.10 Catalyst 0.64 0.39 (50% SHP) gamma-aminopropyl- 1.29 1.45 trihydroxy-silane (2% solution) Water 89.92 89.92 Total (g) 800 800 pH observed 1.9 1.57

Examples 17-20: Binder Preparations with Phosphorus Crosslinkers

The binder compositions set forth in Table 5 were prepared according to the general procedure of Examples 15-16. The pH was measured and given in table 5.

TABLE 5 Binder recipes (weight in percent, except total weight in grams) Example Component Example 17 Example 18 Example 19 20 Maltodextrin 6.44 5.68 11.96 6.44 (as polyol) Diammonium 2.03 2.80 2.99 2.03 Phosphate (as crosslinker) 28% Ammonium 0.06 hydroxide (pH adjuster) gamma- 1.27 1.27 2.24 1.27 aminopropyl- trihydroxy-silane (2% solution) Water 90.25 90.25 82.8 90.2 Total (g) 800 800 800 800 pH observed 2.4 2.363 8.42 10

Example 21: Preparation of Fibrous Product (Handsheet)

Handsheets were made according to the following procedure. To approximately 5 liters of water in a bucket are added 8 drops of NALCO dispersant 01NM159. This dispersion is stirred at a slow speed so as not to produce foam. Wet chop glass fibers (8 grams) are added and allowed to stir for 5 minutes. A screen catch is placed in a 12×12×12 inch 40 liter Williams standard pulp testing apparatus (a.k.a. a “deckle box”) and the box is closed. The deckle box is then filled with water to the “3” mark and a plate stirrer is placed in the deckle box. After the glass fiber water is stirred for about 5 minutes, a 0.5% wt. solution of polyacrylamide, NALCO 7768 (80 grams) is added and stirred at low speed for one minute, after which the stirring speed is increased to the highest setting and allowed to stir for an additional 2 minutes. The glass fiber solution is then immediately dumped into the deckle box and stirred with the plate stirrer for 10 rapid strokes. At this point, the valve on the deckle box is depressed until the deckle box was empty. After the deckle box is drained, the box is opened and the screen with the handsheet is removed from the base by holding opposite corners of the screen.

The screen was then placed on a wooden frame and the binder compositions are applied to the handsheet using a roll coater. Excess binder is vacuumed off. The binder-coated handsheet is placed into an oven for drying and curing, typically for three minutes at 400° F. The handsheet is then cut into one inch strips, which are placed in a desiccator overnight.

Example 22: Properties of Fibrous Product (Handsheets)

Handsheets were made according to the general procedure of example 21 except as noted in Table 6 below. The tensile strength, the Loss on Ignition (LOI), and the tensile strength divided by the LOI (tensile strength/LOI) for each sample was determined under ambient (RT) and steam conditions. The tensile strength was measured using Instron. The loss on ignition (LOI) of the reinforcing fibers is the reduction in weight experienced by the fibers after heating them to a temperature sufficient to burn or pyrolyze the organic size from the fibers. The loss on ignition was measured according to the procedure set forth in TAPPI T-1013 OM06, Loss on Ignition of Fiberglass Mats (2006). To place the handsheet in a steam environment, the handsheets were placed in an autoclave at 240° F. at a pressure between 400 and 500 psi for 30 minutes.

The results of this experiment are set forth in Table 6.

TABLE 6 Properties of Fibrous Products Ex 15 Ex 16 Ex 17 Ex 18 Ex 19 Ex 20 Cure Cycle 450 F. for 450 F. for exceptions 3 min 3 min Tensile 10.1 8.38 5.01 4.6 7.95 2.2  Strength (RT) (lbf) LOI (%) 6.43 4.99 4.24 3.36 3.75 2.26 Tensile/LOI 1.57 1.68 1.18 1.37 2.12 0.97 After Steam 5.76 3.27 4.33 3.88 — — aging Tensile Strength (lbf) After Steam 7.03 5.66 4.38 3.67 — — aging LOI (%) After Steam 0.82 0.58 0.99 1.06 — — aging Tensile/ LOI

In the following examples 23-25, the formula are given in weight percent except total weight is given in grams.

Example 23: Phosphonic Acid Binder Composition

A binder composition is prepared according to the general procedure of Examples 15-16, using the following recipe:

Component Wt % Maltodextrin 6.50 H3PO3 (crosslinker) 1.63 50% H3PO2 (catalyst) 0.63 2% Silane Solution 1.25 Distilled Water 90.00 Total (g) 800

Example 24: Vinylphosphoric Acid Binder Composition

A binder composition is prepared according to the general procedure of Examples 15-16, using the following recipe:

Component Wt % Maltodextrin 6.50 Vinyl Phosphoric Acid 1.63 Azo catalyst 0.02 2% Silane Solution 1.25 Distilled Water 90.61 Total (g) 800 The vinyl portion of the phosphoric acid provides a mechanism for increasing the crosslinking density by free radical reactions, while the phosphoric acid and maltodextrin polyol are free to provide esterification reactions to the phosphodiester linkages.

Example 24: Phosphoric Acid Binder Composition with Synthetic Polyol

A binder composition is prepared according to the general procedure of Examples 15-16, using the following recipe:

Component Wt % 100% Joncryl 804 (BASF) 6.25 85% H3PO4 1.25 2% Silane Solution 1.25 Distilled Water 91.25 Total (g) 800 The BASF JONCRYL® product is a polymeric, synthetic polyol (hydroxyl functionalized polyacrylic acid).

The invention of this application has been described above both generically and with regard to specific embodiments. Although the invention has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the generic disclosure. The invention is not otherwise limited, except for the recitation of the claims set forth below. 

What is claimed is:
 1. A method of making a fibrous product comprising: applying a binder to a pack of randomly oriented fibers, said binder composition comprising: at least one polyol having multiple hydroxyl groups; and at least one polyvalent phosphorus crosslinking agent; and heating the pack to which the binder composition is applied to at least partially cure the binder, wherein the cured binder comprises hydroxyl groups of the polyol crosslinked by phosphodiester linkages.
 2. The method of claim 1, further comprising forming the phosphodiester linkages with a crosslinking agent of formula I

wherein ˜Y represents either a double bonded oxygen or a lone pair of electrons; R¹ and R² are independently selected from OH, OR⁴, O(CO)R⁴, or O⁻M⁺; and R³ is selected from H, OH, R⁴, OR⁴, O(CO)R⁴, O⁻M⁺ or OR⁵; wherein R⁴ is (C₁-C₅)alkyl, (C₁-C₅)alkenyl, (C₁-C₅)alkynyl, or aryl; M⁺ is a cation representing an ionizable salt; and R⁵ represents 1 to 5 additional phosphonate moieties or a polymeric backbone of 1-20 carbons connected to additional phosphonate moieties.
 3. The method of claim 2, wherein the crosslinking agent is selected from acids or ammonium salts of phosphonic acid, phosphorous acid, phosphoric acid, or polyphosphoric acid.
 4. The method of claim 3, wherein the crosslinking agent is an ammonium salt of phosphoric acid, or a polyphosphoric acid.
 5. The method of claim 1, further comprising forming the phosphodiester linkages with a polymeric polyol.
 6. The method of claim 5, wherein said polymeric polyol is selected from polyvinyl alcohol, polyether polyols, polyester polyols, polyacrylic polyols and polysaccharides.
 7. The method of claim 6, wherein said polyol is a water-dispersible polysaccharide selected from the group consisting of pectin, dextrin, maltodextrin, starch, modified starch, starch derivatives and combinations thereof.
 8. The method of claim 7, wherein said polysaccharide is a carbohydrate having a dextrose equivalent number from 2 to
 20. 9. The method of claim 8, wherein the binder further comprises from about 20% to about 99% by weight of the total solids in the binder composition of the at least one carbohydrate polyol; and from about 1% to about 40% by weight of the total solids of the at least one crosslinking agent. 